N-aryl-n&#39;-substituted amino phthalamides



United States Patent 3,502,685 N-ARYL-N-SUBSTITUTED AMINO PHTHALAMIDES Arthur H. Gevirtz, New Haven, Ronald B. Ames, Nauga- "ice The compounds of the present invention may be represented by the general formula:

tuck, and Allen E. Smith, Bethany, Conn., assignors to Uniroyal, Inc., New York, N.Y., a corporation of New 5 Jersey CNHNRi No Drawing. Filed Oct. 20, 1967, Ser. No. 676,695 II I Int. Cl. C07c 103/24, 27/30; A01u 9/20 0 US. Cl. 260294 7 Claims where Ar is naphthyl, particularly a-naphthyl, the chloro- 10 substituted phenyls, such as diand trichlorophenyl, and R, and R may be hydrogen or lower alkyl having 1 to ABSTRACT OF THE DISCLOSURE 5 carbon atoms or compositely form a nonaromatic Chemical compounds having the general formula heterocycle, or if R is hydrogen, R is phenyl or naphthyl or chlorosubstituted derivatives thereof. Examples of R H and R are methyl, isopropyl, butyl, (CH CH O, C-NHAr tetramethylene, pentarnethylene, or hexamethylene.

The aforesaid compounds are prepared by reaction of fiJ-NHI]I-Ri N-arylphthalimides with 1 to 2 equivalents of the desired R2 hydrazine according to procedures known to those exwhere Ar is naphthyl, dichlorophenyl or trichlorophenyl, pe-nenceci m i' The Ieactlon may be earned. i and R1 and R2 are hydrogen or lower alkyl or compositely uslng an inert so vent such as water, methanol, acetomtrlle with the nitrogen atom form a heterocyclic ring or if R1 as a reactlon mgdrum. Thereactlon can be carried out is hydrogen, R2 is phenyl or naphthyl These compounds at room or re ux tempe1atures depending upon the are useful as herbicides. nature of the hydrazine The following example illustrates the preparatlon of the compounds of the invention: h'lllhils invention relates to N-aryl-N'-subsituted amino EXAMPLE I p t a amides and their use as herbicides, articular] as pre emergem herbicidesp y N (1 naphthyl) N (am1no)phthalam1de Controlling weeds in certain agricultural crops without 14 p ynp h l m e injuring the crop is a unique problem. Many herbicides Were added to 300 mL of acctonitrile and 28 will control weeds without injury only under optimum 111016) of anhydrous hydrazine Wfire added with conditions, Herbi id applied over a large geographical stirring. Within 2 minutes new solid formation occurred. area seldom have optimum conditions to work. Under The IniXtllre was Stirred one hour to insure complete adverse conditions, such as heavy rainfalls or very dry reaction P filtration gof White Solid soil conditions, pre-emergent herbicides will give erratic M.P. 140-141 (dec.) were obtained. An infrared p cperformance. N-l-naphthylphthalamic acid, awell known trllIn Showed the Presence of moderate bands at pro-emergent herbicide, performs well under optimum 3.08, 3-13 and 7 and Strong bands at conditions in that it controls weeds without injurin the 6.32 4 compatible with the desired compound. crop. Under Wet or heavy rainfall conditions, N-l- A representative list of compounds prepared by this naphthyl phthalamic acid will move downward through method and representative of the present invention are the soil into the germinating crop seed zone and cause described in Table I.

TABLE I Calculated Found Empirical Percent Percent Percent Percent Percent Percent Ar R; R M.P., formula C H C H N 2, 3-diehlorophenyl Methyl Methyl 1 100 l-naphthyl do do 193-5 Dn Hydr Hydroge 1 140-1 0 11 91 0 70.81. 4. 95 13.76 69.86 4.93 14.32 DO d0 PhenyL 214-5 C27Hg1N303 75.57 5.02 0 76.45 4.73 11.30 D0 Penta-methylene 205-6 CZQHQQNQO 73.97 6. 21 1 5 0 6. -8 Do (CH2CH2)2O 1217-3 G H N O 70.38 5. 64 11.19 70.58 5.65 11.57 3, fi-dichlorophenyl Hydrogen Hydrogen... 1 1323 l Decanoate. considerable injury. The present invention is unique in that, by converting the carboxyl grOup of N-l-naphthyl phthalamic acid to a hydrazide group, leaching is virtually eliminated. This is a desirable discovery for two reasons: firstly, the chemical stays in the germinating weed seed Zone, facilitating weed control; and secondly, the chemical is less likely to injure the crop seed germination since this zone is below the weed seed zone. To initiate this activity, phthalamides may be applied to the soil at, before or after crop emergence and before weed emergence.

The chemicals of the present invention may be applied to soil at, before or after crop emergence and before weed emergence. The chemicals may be applied to soil in various forms as explained below.

The chemical may be impregnated on granular organic and inorganic carriers such as corncobs, activated carbon, attapulgite clay, mica and other types of granular carriers known in the art. They may also be pelletized as described by Gallaway Patent No. 3,056,723 or by Polon Patent No. 3,192,290. If desired, the chemicals may be mixed with a powdered solid carrier, together with a surface active dispersing agent, so that a wettable powder may be obtained which may be applied directly, or which may be shaken up Withlwvater tomake an aqueous dispersion for application that form. The chemical's may be dissolved in aliphatic and aromatic hydrocarbons, and the solution of the chemical dispersed in water with the aid of a surface-active dispersing agent to give a' sprayable aqueousdispersion. Such surface-active dispersing agents may be anionic, nonionic or cationic surface active agents. Such surface-active agents are'well known and reference is made to Hoffman et al., US. Patent No, 2,6 I4,9l6, columns 2 to 4, for detailed examples of the same. 7

The chemicals, in the forms listed above, may be applied (1) to the surface and (2) to soil surface and incorporated to a depth of /2 to 2".

The chemicals may be applied tothe soil at rates of 1 to pounds/acre, preferably, up to 20 pounds/acre. f To illustrate more fully the herbicidal use of the compounds of the instant invention, attention is directed to H the following example:

EXAMPLE II One hundred and fifty mg. of each chemical were ground and blended with mg. of a wettable powder containing 4% Triton X (alkylaryl polyether alcohol) OPE9-l0, 4% Daxad l1 (alkylnaphtholene sodium sulfonate) and 92% Dixie clay (inert). This mixture was made :up to 300 ml. with H O, giving a 500 ppm. solution. Forty and eighty ml. of the 500 ppm. solution were made to 160 :ml. with H O to give two solutions containing and 250 ppm. solution respectively. Eighty mls. of each concentration were drenched on a mm. pot EWhiCh contained a mixture of four broadleaf Weeds? namely: pigwcedAmarant/ws retroflexus, purslane Portulaca Qieracea, Lambs-quarters Chenop0diuml aibum and oxeye daisyChrysanthemum leucanthemum. Also in the pot were three grass species, namely: crabgrass-Digimria sanguinalis, barnyard grass-Echinochiea crusgalli and giant foxtail-Setaria faberii. Eighty ml. of the remaining concentrations were applied as replications. Eighty ml. of the three concentrations, 125, 250 and 500, as applied are equal to 5, 10 and 20 pounds per acre. Pots were subirrigated and scored 14 days later. Table H illustrates the herbicidal activity of the compounds of the invention: 7 a 7 TABLE II it 7 Percent control at- Injury to the soybean plants was measured as percent stunting as compared to control as well as percent occurrence of negative geotropic type injury. Results are given in Table III:

*'The above data clearly show that the compounds of the invention are far less injurious to plants than the most closely related compound of the prior, viz, the N-(1-naphthyl)phthalamic' acid listed last in Table III. Having thus described our invention, what we claim and desire to protect by Letters Patent is: 1. A compound having the formula where Ar is naphthyl, dichlorophenyl or trichlorophenyl and R and R are hydrogen or lower alkyl having 1 to 5 carbon atoms or compositely form, with the N atom to which they are bonded, a piperidino or a morpholino rim or, when R is hydrogen, R is phenyl.

2. The compound of claim 1 wherein Ar is u-naphthyl.

3. The compound of claim 1: N-(1-naphthyl)-N'- (amino)phthalamide.

4. The compound of claim 1: N-(2,3-dichlorophenyl)- N'-(dimethylamino)phthalamide. Y

5. The compound of claim 1: N-(1-naphthyl)-N-(dimethylamino)phti1alamide.

6. The compound of claim 1: N-(l-naphthyl)-N-(anilino)-phthalamide.

7. The compound of claim 1: N-(l-naphthyl)-N'-(pi- I peridino)-phthalarnide.

References Iited UNITED STATES PATENTS 3,429,877 2/1969 Maeder et a1 260558 HElf-YRY R. nLEs, Primary Examiner H. I. MOATZ, Assistant Examiner US. Cl. X.R. 

